CN103232031A - Method for treating waste polyolefin plastics - Google Patents
Method for treating waste polyolefin plastics Download PDFInfo
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- CN103232031A CN103232031A CN2013101396834A CN201310139683A CN103232031A CN 103232031 A CN103232031 A CN 103232031A CN 2013101396834 A CN2013101396834 A CN 2013101396834A CN 201310139683 A CN201310139683 A CN 201310139683A CN 103232031 A CN103232031 A CN 103232031A
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Abstract
The invention discloses a method for treating waste polyolefin plastics, which is characterized by comprising the following steps: adding waste polypropylene, ferrocene and sodium azide into a high-pressure kettle, heating to 580-620 DEG C, reacting for 8-24 hours, washing the product with ethanol and water, performing centrifugal separation, and drying to obtain a spongy iron/carbon nanotube composite material, wherein the mass ratio of the waste polypropylene, the ferrocene and the sodium azide is 1:1:(0.25-10). According to the invention, waste polyethylene can be completely decomposed, thus causing no environment pollution; and the yield of the prepared spongy iron/carbon nanotube composite material is up to 90% or above.
Description
Technical field
The present invention relates to the method that a kind of catalytic decomposition technology prepares iron/carbon nano tube compound material, belong to the waste polyolefine plastics processing technology field.
Background technology
Advantage such as polyolefin plastics has that quality is light, intensity is high, good heat resistance, price are low, thus the effect of not replacing had in daily life, and consumption is huge.But its a large amount of waste or used plastics that brought enormous amount that use cause severe contamination to environment, thereby influence people's life.Therefore, how effectively handling the polyolefin plastics waste is a research focus.Because polyolefin plastics can not biological degradation, to handle be invalid so bury.Though incinerating can be with waste or used plastics as thermal source, rate of utilization is too low, fails effectively to utilize.People wish waste or used plastics is converted into more valuable material.Existingly waste or used plastics is processed recycling relate to a large amount of collections, transportation, separation and recovery system, the course of processing comprises densification, grinding, pulverizing, mixing, the process complexity, and can not obtain the homogeneous material of quality products.
Therefore, people are seeking a kind of waste or used plastics treatment process of maturation, the solid carbonaceous material that waste or used plastics is decomposed into low-molecular-weight product or has the important application prospect, for example the matrix material of carbon nanotube, carbosphere and carbon will be reduced to minimum to the influence of environment when striving for maximum profit.For example, pyrolysis method can be decomposed into waste or used plastics low-molecular-weight material [J.Anal.Appl.Pyrolysis 81,7 (2008); Waste Manag.29,2625 (2009) .]; Yet products therefrom is the mixture of different molecular weight compound, and temperature of reaction is higher than 600 ℃, even up to 900 ℃, [J.Anal.Appl.Pyrolysis 86,260 (2009) for the energy consumption height; Fuel Process Technol.91,277 (2010) .].People such as Kartel report, under the sulfuric acid existence condition, adopting thermal treatment and steam activation technology waste or used plastics can be degraded into specific surface area is 1030m
2The activated carbon of/g [Carbon 44,1019 (2006) .], however productive rate has only 22%.Recently, some investigators adopt the solventless one-step method that waste or used plastics (as: polyethylene, polyethylene terephthalate, polypropylene, polystyrene) is converted into carbon material (carbon ball and carbon nanotube) [Green Chem.11,448 (2009); Ind.Eng.Chem.Res.48,1484 (2009); J.Environ.Monit.12,455 (2010); Environ.Sci.Technol.44,4753 (2010) .], this method effectively and can mass-producing, but temperature of reaction is higher.
The report of C-base composte material that at present waste or used plastics is converted into magnetic functionization is less, particularly iron/carbon composite.
Summary of the invention
Treatment temp height, the product that exists at prior art processing waste plastic can not take full advantage of, secondary pollution problem, the present invention propose a kind of in enclosed system catalytic decomposition handle the method for waste polyolefine plastics, have decomposition efficiency height, productive rate height, characteristics that the degradation production using value is big.
Technical scheme of the present invention is:
A kind of method of handling waste polyolefine plastics is that waste and old polypropylene, ferrocene and sodiumazide are added in the autoclave, and temperature rises to 580~620 ℃, reacted 8~24 hours, product washs successively with the second alcohol and water, and is centrifugal and dry, namely obtains sponge iron/carbon nano tube compound material.
Waste and old polypropylene, ferrocene and sodiumazide are pressed mass ratio 1:1:0.25~10;
The mass ratio of waste and old polypropylene, ferrocene and sodiumazide is preferably 1:1:0.25~5, because in this scope, the one-tenth efficiency of carbon conversion of waste and old polypropylene is more than 90%, and wherein the production rate of sponge iron/carbon nano tube compound material is more than 60%;
The mass ratio of waste and old polypropylene, ferrocene and sodiumazide is more preferred from 1:1:0.5~2.5, because in this scope, the one-tenth efficiency of carbon conversion of waste and old polypropylene is more than 94%, and wherein the production rate of sponge iron/carbon nano tube compound material is more than 80%;
Reaction principle is as follows:
NaN
3→Na+N
2 (1)
Fe(C
5H
5)
2→Fe+10C+5H
2 (2)
PP+Fe→C+H
2+Fe (3)
1. the present invention adopts the catalytic decomposition technology, in closed system, under the regulation and control of sodiumazide, waste polyolefine plastics substantially all is converted into spongiform iron/carbon nano tube compound material, temperature of reaction is low than prior art, reaction process is simple and easy to control, and products therefrom has that magnetic, pattern are good, pollution-free, productive rate is more than 90%.
2. sponge iron/carbon nano tube compound material of obtaining of method of the present invention, length of carbon nanotube is about 3.5 μ m, and diameter is about 30 nanometers, and the size of iron nano-particle is about 44 nanometers.
Description of drawings
Fig. 1 is the X-ray powder diffraction spectrogram of the sponge iron/carbon nano tube compound material of embodiment 1 preparation.
Fig. 2 is the Raman spectrogram of the sponge iron/carbon nano tube compound material of embodiment 1 preparation.
Fig. 3 be embodiment 1 preparation sponge iron/carbon nano tube compound material low power field emission scan photo.
Fig. 4 be embodiment 1 preparation sponge iron/carbon nano tube compound material high power field emission scan photo.
Fig. 5 be embodiment 1 preparation sponge iron/carbon nano tube compound material the transmission electron microscope photo.
Fig. 6 be embodiment 1 preparation sponge iron/carbon nano tube compound material the element dispersion spectrum.
Fig. 7 is the magnetic hysteresis loop of the sponge iron/carbon nano tube compound material of embodiment 1 preparation.
Embodiment:
Specify technical scheme of the present invention below with reference to embodiment.
Embodiment 1:
With 1 gram waste and old polypropylene (model: F401), 1 gram ferrocene (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) and 1 restrains sodiumazide (Shanghai Chemical Reagent Co., Ltd., Sinopharm Group) and join one 20 milliliters stainless steel autoclave (this reactor is not with tensimeter, pressure in the reaction process in the still decomposes generation by reactant, in whole process, pressure constantly changes.In the process of the heat temperature raising after autoclave cuts out, form high pressure in the autoclave gradually, but this parameter is not significant parameter, perhaps must be limited in the data scope) in, put into after sealing can temperature programming electric furnace, furnace temperature was raised to 600 ℃ from room temperature in 120 minutes, naturally cooled to room temperature then after keeping 12 hours under 600 ℃.Final product in the autoclave comprises the settling of black and residual gas.Collect with distilled water and absolute ethanol washing repeatedly being bonded at black deposit on the still wall internal surface, the sample that obtains after the filtration, sample respectively in vacuum drying oven in 50 ℃ of dryings 4 hours, collect for sign at last.
Adopt Japanese Rigaku D/max-γ A type X-ray powder diffraction (XRD) instrument powder to be carried out material phase analysis, Cu K α
Graphite monochromator, pipe is pressed and electric current is respectively 40kV and 20mA, 10.0 ° of min of sweep velocity
-1
Fig. 1 is the X-ray diffraction spectra of the product of embodiment 1 preparation.As seen from Figure 1,2 θ have 3 stronger diffraction peaks at 10-80 ° in the x-ray diffraction spectra, wherein the sharp-pointed diffraction peak of diffracted intensity height and peak shape can be demarcated and is the iron of body-centered cubic phase (JCPDS card No.06-0696), and intensity diffraction peak low and broadening can be the graphite (JCPDS card No.41-1487) of six side's phases by demarcation near about 25 °, other impurity peaks do not occur.
Raman spectrum is handled by Spex 1403 type Raman spectrometers, and using wavelength is the Argon ion laser of 514.5 nanometers, and powder is further confirmed.Fig. 2 is the Raman spectrogram of product.Can observe two Raman peaks clearly among the figure, lay respectively at 1596cm
-1And 1346cm
-1, corresponding to the feature Raman peaks of graphitized carbon nano structure.Be positioned at 1596cm
-1Peak (G band) corresponding to the E in the two-dimentional graphite linings
2gVibration modes, the sp in this peak and two-dimentional hexagonal mesh
2The carbon atom vibration of hydridization is relevant; Be positioned at 1346cm
-1Peak (D band) relevant with the vibration that the two dimensional surface edge has the random carbon atom of outstanding key; Strong D band peak shows that there is defective in the crystal face of carbon nanotube.
Use the pattern, particle size of field emission scanning electron microscope (FESEM, JEOL JSM-6300F) and transmission electron microscope (HRTEM, JEOL 2010, acceleration voltage is 200kV) observation product etc.; Use the element scattering spectra that the composition of product is done further affirmation.
From field emission scan photo Fig. 3 of product as seen, adopt the productive rate of sponge iron/carbon nano tube compound material that the inventive method obtains up to 94%; Fig. 4 is the field emission scan photo that amplifies, and the result shows that it is 3.5 μ m that the carbon nanotube in sponge iron/carbon nano tube compound material is about, and diameter dimension is even; Fig. 5 is the transmission electron microscope photo of sponge iron/carbon nano tube compound material, and the result shows that its carbon nanotube diameter is about 30nm, and the size of iron nano-particle is about 44nm; The element scattering spectra of Fig. 6 sponge iron/carbon nano tube compound material, the result shows that product comprises carbon and two kinds of elements of iron, has proved that further product is the matrix material of iron and carbon.
(MPMS5, Quantum Design) measures the magnetic property of sponge iron/carbon nano tube compound material by superconducting quantum interference device (SQUID) (SQUID), and measuring temperature is 298K, and intensity is 10000Oe.
Under the room temperature condition, in magnetic field be-10000Oe in the scope of 10000Oe, investigate the magnetic property of sponge iron/carbon nano tube compound material, the result as shown in Figure 7.Magnetic hysteresis loop shows that spongiform iron/carbon nano tube compound material has ferromagnetic property, and its saturation magnetization rate and coercive force are respectively 63.1emu/g and 186.1Oe.From characterization result as can be seen, with saturation magnetization rate and coercive force (the 220emu g of block iron
-1, 0.9Oe) to compare, the saturation magnetization rate of sponge iron/carbon nano tube compound material is lower than the saturation magnetization rate of block iron, and major cause is because the existence of carbon nanotube; In addition, the coercive force of this sponge iron/carbon nano tube compound material is bigger than the coercive force of block iron, mainly is because different size and patterns causes.
Analyze to confirm that more than can obtaining consistent appearance, size by the catalytic decomposition waste and old polypropylene, evenly to reach output be spongiform iron/carbon nano tube compound material of 94%.
Embodiment 2:
Difference from Example 1 is, waste polyolefine, ferrocene and sodiumazide are joined the amount of 1:1:10 in the stainless steel autoclave of a 20mL by mass ratio, gained iron/carbon composite productive rate is 95%, but the productive rate of sponge iron/carbon nano tube compound material is about 60%, basic parameter: the length that the median size size of iron particle is about 65nm, carbon nanotube is about 3 μ m, and the diameter of carbon nanotube is about 57nm.
Embodiment 3:
Difference from Example 1 is, by mass ratio the amount of 1:1:5 joined waste and old polypropylene, ferrocene and sodiumazide in one 20 milliliters the stainless steel autoclave.Gained iron/carbon composite productive rate is 96%, but the productive rate of sponge iron/carbon nano tube compound material is about 82%, basic parameter: the median size size of iron particle is about 65nm, and the length of carbon nanotube is about 3.2 μ m, and diameter is about 58nm.
Embodiment 4:
By mass ratio the amount of 1:1:0.5 is joined waste and old polypropylene, ferrocene and sodiumazide in one 20 milliliters the stainless steel autoclave, put into after sealing can temperature programming electric furnace.Gained iron/carbon composite productive rate is 95%, but the productive rate of sponge iron/carbon nano tube compound material is about 88%, basic parameter: the length that the median size size of iron particle is about 40nm, carbon nanotube is about 4.5 μ m, and the diameter of carbon nanotube is about 28nm.
The raw material that embodiment 5-9 adopts and the performance perameter of products therefrom see Table 1:
Claims (4)
1. method of handling waste polyolefine plastics, it is characterized in that it being that waste and old polypropylene, ferrocene and sodiumazide are added in the autoclave, be heated to 580~620 ℃, reacted 8~24 hours, product ethanol and water washing, centrifugation and drying namely obtain spongiform iron/carbon nano tube compound material.
2. the method for processing waste polyolefine plastics according to claim 1, the mass ratio that it is characterized in that described waste and old polypropylene, ferrocene and sodiumazide is 1:1:0.25~10.
3. the method for processing waste polyolefine plastics according to claim 1, the mass ratio that it is characterized in that described waste and old polypropylene, ferrocene and sodiumazide is 1:1:0.25~5.
4. the method for processing waste polyolefine plastics according to claim 1, the mass ratio that it is characterized in that described waste and old polypropylene, ferrocene and sodiumazide is 1:1:0.5~2.5.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104945622A (en) * | 2015-06-01 | 2015-09-30 | 西南科技大学 | Novel ferrocene based flame retardant char-forming polymer and preparation method thereof |
CN107520464A (en) * | 2017-09-01 | 2017-12-29 | 江苏科技大学 | A kind of method for preparing iron nano-particle/major diameter carbon nano tube compound material |
CN111085169A (en) * | 2019-12-23 | 2020-05-01 | 华东师范大学 | Porous carbon adsorbent based on polyethylene micro-plastic and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101239713A (en) * | 2008-03-04 | 2008-08-13 | 江苏大学 | Method of preparing multi-wall carbon nano-tube by using polymer as raw material |
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CN101239713A (en) * | 2008-03-04 | 2008-08-13 | 江苏大学 | Method of preparing multi-wall carbon nano-tube by using polymer as raw material |
Non-Patent Citations (1)
Title |
---|
DEHUI DENG ET AL.: "Iron Encapsulated within Pod-like Carbon Nanotubes for Oxygen Reduction Reaction", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104945622A (en) * | 2015-06-01 | 2015-09-30 | 西南科技大学 | Novel ferrocene based flame retardant char-forming polymer and preparation method thereof |
CN107520464A (en) * | 2017-09-01 | 2017-12-29 | 江苏科技大学 | A kind of method for preparing iron nano-particle/major diameter carbon nano tube compound material |
CN111085169A (en) * | 2019-12-23 | 2020-05-01 | 华东师范大学 | Porous carbon adsorbent based on polyethylene micro-plastic and preparation method and application thereof |
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